CN108473899A - The lubricating composition of Sulfide-containing Hindered 5-substituted phenol compounds - Google Patents

The lubricating composition of Sulfide-containing Hindered 5-substituted phenol compounds Download PDF

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CN108473899A
CN108473899A CN201680072001.4A CN201680072001A CN108473899A CN 108473899 A CN108473899 A CN 108473899A CN 201680072001 A CN201680072001 A CN 201680072001A CN 108473899 A CN108473899 A CN 108473899A
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butyl
lubricating composition
alkyl
thioether
phenol
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张琰湜
J·J·汉索恩
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Lubrizol Corp
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Lubrizol Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M135/26—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M135/24—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2040/251—Alcohol fueled engines
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Abstract

The purposes of thioether fortified phenol and thioether fortified phenol, the thioether fortified phenol is thioether substituted alcohols or thioether replaces the reaction product of amine and the phenol at least one side acyl group and at least 1:1 methylthio group:Phenolic groups ratio.By making internal combustion engine be contacted by the method for lubricating internal combustion engines with the lubricating composition comprising thioether fortified phenol.The method that the deposit in engine forms and/or corrodes is reduced using the lubricating composition comprising thioether fortified phenol.

Description

The lubricating composition of Sulfide-containing Hindered 5-substituted phenol compounds
Invention field
Disclosed technical field relates generally to the lubricating composition of the oxybenzene compound comprising Sulfide-containing Hindered.
Background of invention
Recently, new engine test such as Mack T13 are developed and are testing higher temperature than previous engine to measure Under oxidation.Think the higher temperature undergone in these new more preferable simulation modern heavy-duty (" HD ") diesel engines of experiment.However, this A little higher temperatures impose engine oil formulations the oxidation stress of bigger.Therefore, it is contemplated that conventional engines oil antioxidant, packet The handling rate for including phenol and amine antioxidants improves.In the case of amine antioxidants, handling rate can be improved ten times equally It is more.
The raising of handling rate can negatively affect performance of the lubricant in other fields, such as abrasion, friction, coal smoke are heavy Product object, acid formation, corrosion or sealing wear, making it difficult to meet the oxidation regulation of engine oil, while also meet about other The regulation that performance such as deposit and acid are formed.As used herein, unless otherwise expressly stated, total base number (" TBN ") passes through ASTM D2896 the methods measure.
Summary of the invention
However, surprisingly it has been found that compared with known phenolic antioxidants, thioether fortified phenol (" thioether-phenol " or " sulphur Ether-phenol ") show improved antioxygenic property, while reducing deposit and being formed.Therefore, in one embodiment, open Include the lubricating composition of oil and thioether fortified phenol (" thioether-phenol ") with lubricant viscosity.Thioether-phenol may include Thioether substituted alcohols or thioether replace the reaction product of amine and the phenol at least one side acyl group and can be at least 1:1 Methylthio group:Phenolic groups ratio.
In one embodiment, thioether-phenol can have such as the structure in formula (I)：
Wherein m is the integer of 0-3；N is the integer of 1-2；P is the integer of 1-20；Each R1It independently is hydrogen or C1-C20Hydrocarbon Base, or when m be more than 1 when, two alkyl together when can form saturation or unsaturation ring containing 5-6 carbon atom；R2For C1-C6Alkyl；R3For C1-C20Alkyl；R4For C1-C32Alkyl；X is O (oxygen atom) or NR5(nitrogen-atoms with alkyl)；And R5 For hydrogen or C1-C24Alkyl, condition are when X is NR5When, then p is 1.
In another embodiment, at least one R1Can be C1-C4Alkyl.In yet another embodiment, R3Can be C1- C20Alkyl, the integer that X is O (oxygen) and p is 1-12.
In another embodiment, lubricating composition may include with thioether-phenol such as the structure in formula (II)：
Wherein R3For C1-C20Alkyl；R4For C1-C32Alkyl；R6For hydrogen or C1-C12Alkyl；And R7And R8Independently be hydrogen or C1-C20Alkyl or when together, R7And R8Saturation or unsaturation ring containing 5-6 carbon atom can be formed.
In one embodiment, R6And R7At least one of can be tertiary butyl.In yet another embodiment, R6With R7Can all be tertiary butyl.In another embodiment, R4Can be C1-C18Alkyl.In yet another embodiment, R3Can be C2-C4Alkyl.
In another embodiment, thioether-phenol may include following at least one：3- (3,5- di-t-butyl -4- oxybenzenes Base) propionic acid 2- (butylthio) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (butylthio) propyl ester, 3- (bis- uncles of 3,5- Butyl -4- hydroxyphenyls) propionic acid 2- (butylthio) butyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (own sulfenyl) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (own sulfenyl) propyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (own sulfenyl) butyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (pungent sulfenyl) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyls Phenyl) propionic acid 2- (pungent sulfenyl) propyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (pungent sulfenyl) butyl ester, 3- (3,5- bis- Tertiary butyl -4- hydroxyphenyls) propionic acid 2- (last of the ten Heavenly stems sulfenyl) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (last of the ten Heavenly stems sulfenyl) third Ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (last of the ten Heavenly stems sulfenyl) butyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (dodecylthio) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (dodecylthio) propyl ester or 3- (3, Or mixtures thereof 5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (dodecylthio) butyl ester,.Lubricating composition may include based on profit The weight % thioethers of 0.01 weight % of total weight to 5-phenol of sliding composition.
In one embodiment, lubricating composition can further include at least one nitrogenous dispersant.In other implementations In scheme, lubricating composition can further include at least one overbased detergent.
The method for also disclosing lubricating internal combustion engines.This method includes making internal combustion engine and comprising thioether substituted benzene as described above The lubricating composition of phenol (" thioether-phenol ") contacts.Thioether-phenol can be thioether fortified phenol or thioether replaces amine and has The reaction product of the phenol of at least one side acyl group.Methylthio group and the ratio of phenolic groups can be at least 1:1.
Also disclose purposes of the thioether-phenol in lubricating composition as described above.Thioether-phenol can be used for reducing oxygen Change, reduce the total base number (TBN) that deposit formed and/or assisted in keeping lubricating composition.
Also disclose the method that the deposit in internal combustion engine forms and/or corrodes that reduces.This method may include making internal combustion engine It is contacted with the lubricating composition comprising thioether fortified phenol as described above (" thioether-phenol ").
Detailed description of the invention
Above-mentioned each file is herein incorporated by reference, including any previous application claimed priority, nothing By whether being specifically set forth in above.Referring to for any file is not to recognize that this document obtains the qualification of the prior art or with any power Limit constitutes the common sense of technical staff.Except embodiment China and foreign countries, or if in addition explicitly pointed out, be described material in the specification The quantity of amount, reaction condition, molecular weight, carbon atom number etc. should be understood as modifying by wording " about ".It should understand that this paper institutes The upper and lower bound of the amount of stating, range and ratio can be combined independently.Similarly, the range and amount of each element of the present invention can with it is any The range or amount of other elements are used together.
As used herein, be with " comprising ", " containing " or " being characterized in ... " synonymous transitional term "comprising" it is inclusive or It is open and be not excluded for other unstated elements or method and step.However, herein in each description of "comprising", it is intended to As optional embodiment, which further includes phrase " substantially by ... form " and " Consists of ", wherein " Consists of " are not Including any element not described or step, " substantially by ... form " allows to include composition that substantial effect is not considered Or the other of the basic and new features of method do not describe element or step.
Each feature and embodiment are described below by non-limiting description and embodiment.In one embodiment, Disclose the lubricating composition for including oil and thioether fortified phenol (" thioether-phenol ") with lubricant viscosity.Thioether-phenol packet Reaction or the condensation product of Sulfide-containing Hindered substituted alcohols or thioether substitution amine and the phenol at least one side acyl group.Thioether-phenol It may include the reaction product of mercaptan and phenol.
Suitable thioether substituted alcohols include but not limited to 2- (butylthio) ethyl alcohol, 2- (butylthio) propyl alcohol, 2- (butylthio) Butanol, 2- (own sulfenyl) ethyl alcohol, 2- (own sulfenyl) propyl alcohol, 2- (own sulfenyl) butanol, 2- (pungent sulfenyl) ethyl alcohol, 2- (pungent sulfenyl) third Alcohol, 2- (pungent sulfenyl) butanol, 2- (last of the ten Heavenly stems sulfenyl) ethyl alcohol, 2- (last of the ten Heavenly stems sulfenyl) propyl alcohol, 2- (last of the ten Heavenly stems sulfenyl) butanol, 2- (dodecylthio) Ethyl alcohol, 2- (dodecylthio) propyl alcohol, 2- (dodecylthio) butanol etc..Suitable phenol includes 3- (3,5- di-t-butyls -4- Hydroxyphenyl) propionic acid, 3- (3,5- di-t-butyl -4- hydroxyphenyls) methyl propionate, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid second Ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propyl propionate, 3- (3,5- di-t-butyl -4- hydroxyphenyls) butyl propionate, 3- (3, 5- di-t-butyl -4- hydroxyphenyls) hexyl propionate etc..
In one embodiment, thioether-phenol can have at least 1:1 methylthio group:Phenolic groups ratio.In other implementations In scheme, thioether-phenol can have at least 1:1-2:1 sulphur:Phenolic groups ratio.
In one embodiment, thioether-phenol can have such as the structure in formula (I)：
Wherein m is the integer of 0-3；N is the integer of 1-2；P is the integer of 1-20；Each R1It independently is hydrogen or C1-C20Hydrocarbon Base, or when m be more than 1 when, two alkyl together when can form saturation or unsaturation ring containing 5-6 carbon atom；R2For C1-C6Alkyl；R3For C1-C20Alkyl；R4For C1-C32Alkyl；X is O (oxygen atom) or NR5(nitrogen-atoms with alkyl)；And R5 For hydrogen or C1-C24Alkyl, condition are when X is NR5When, then p is 1.
In another embodiment, at least one R1Can be C1-C4Alkyl.In yet another embodiment, R3Can be C1- C20Alkyl, the integer that X is O (oxygen) and p is 1-12.
As used herein, term " hydrocarbyl substituent " or " alkyl " are made with its common meaning well known to those skilled in the art With.Specifically, it refers to the group with the carbon atom being connected directly between on molecule rest part and mainly with hydrocarbon property.Hydrocarbon The example of base includes：
Hydrocarbon substituent, i.e., aliphatic (such as alkyl or alkenyl), alicyclic (such as naphthenic base, cycloalkenyl group) substituent group, and virtue Race-, aliphatic series-and alicyclic substituted aromatic substituent and its middle ring complete (such as two by another part of the molecule Substituent group forms ring together) cyclic substituents；
Substituted hydrocarbon substituent contains the non-alkyl for the main hydrocarbon property for not changing substituent group in the context of the present invention Group (such as halogen (especially chlorine and fluorine), hydroxyl, alkoxy, sulfydryl, alkyl thiol, nitro, nitroso and sulfinyl (sulphoxy)) substituent group；
Miscellaneous substituent group, i.e., in the context of the present invention, in the ring being made of carbon atom while with main hydrocarbon property Or contain the substituent group different from carbon, including substituent group such as pyridyl group, furyl, thienyl and imidazole radicals in chain.Hetero atom packet Include sulphur, oxygen and nitrogen.Generally, for every 10 carbon atoms, no more than 2 in alkyl, or not more than 1 nonhydrocarbon takes Dai Ji；Alternatively, substituents may not be present in alkyl.
In yet another embodiment, thioether-phenol can have such as the structure in formula (II)：
Wherein R3For C1-C20Alkyl；R4For C1-C32Alkyl；R6For hydrogen or C1-C12Alkyl；And R7And R8Independently be hydrogen or C1-C20Alkyl or when together, R7And R8Saturation or unsaturation ring containing 5-6 carbon atom can be formed.
In one embodiment, R6And R7At least one of can be tertiary butyl.In yet another embodiment, R6With R7Can all be tertiary butyl.In another embodiment, R4Can be C1-C18Alkyl.In yet another embodiment, R3Can be C2-C4Alkyl.
In another embodiment, thioether-phenol may include following at least one：3- (3,5- di-t-butyl -4- oxybenzenes Base) propionic acid 2- (butylthio) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (butylthio) propyl ester, 3- (bis- uncles of 3,5- Butyl -4- hydroxyphenyls) propionic acid 2- (butylthio) butyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (own sulfenyl) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (own sulfenyl) propyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (own sulfenyl) butyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (pungent sulfenyl) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyls Phenyl) propionic acid 2- (pungent sulfenyl) propyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (pungent sulfenyl) butyl ester, 3- (3,5- bis- Tertiary butyl -4- hydroxyphenyls) propionic acid 2- (last of the ten Heavenly stems sulfenyl) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (last of the ten Heavenly stems sulfenyl) third Ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (last of the ten Heavenly stems sulfenyl) butyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (dodecylthio) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (dodecylthio) propyl ester or 3- (3, Or mixtures thereof 5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (dodecylthio) butyl ester,.
In other embodiments, thioether-phenol may include at least one tool there are one with thioether-phenol of lower structure：
Lubricating composition may include the 0.01 weight % of total weight based on lubricating composition to 5 weight % thioethers-phenol.Make For selection, thioether-phenol can exist with following range：0.01-3 weight %；0.01-1 weight %；0.01-0.5 weight %； Or 0.05-0.1 weight %.Unless otherwise stated, the amount of each chemical constituent, which is expressed as eliminating, usually may be present in quotient Any solvent in industry material or flux oil are based on active chemical.However, unless otherwise stated, eachization being mentioned above Product or composition should be understood as may include isomers, by-product, derivative and usually should understand that be present in commerical grade Other this kind of materials commercial grade material.
In addition to above-mentioned antioxidant, lubricating composition may include one or more additives.In one embodiment, moisten Sliding composition can further include at least one nitrogenous dispersant.In other embodiments, lubricating composition can be wrapped further Containing at least one overbased detergent.In other embodiments again, lubricating composition can further include corrosion inhibitor.
Lubricating composition may include antiwear additive.In one embodiment, antiwear additive may include with a certain amount of existing phosphorus So that lubricating composition has at least 300ppm phosphorus of the total weight based on lubricating composition.
In another embodiment, lubricating composition may include at least one boron-containing compound.Exemplary boron-containing compound Including but not limited to borate, boric acid ester alcohol or combinations thereof.
The method for also disclosing lubricating internal combustion engines.This method may include that internal combustion engine is made with comprising thioether as described above to replace The lubricating composition of phenol (" thioether-phenol ") contacts.Thioether-phenol can be that thioether fortified phenol or thioether replace amine and tool There is the reaction product of the phenol of at least one side acyl group.Methylthio group and the ratio of phenolic groups can be at least 1:1.
Also disclose purposes of the thioether-phenol in lubricating composition as described above.Thioether-phenol can be used for reducing oxygen Change, reduce the total base number (TBN) that deposit formed and/or assisted in keeping lubricating composition.
Also disclose the method that the deposit in internal combustion engine forms and/or corrodes that reduces.This method may include making internal combustion engine It is contacted with the lubricating composition comprising thioether fortified phenol as described above (" thioether-phenol ").
Oil with lubricant viscosity
Including the lubricating composition of thioether-phenol described herein can be used for having in the oil of lubricant viscosity.This kind of oil includes Natural and synthetic oil, derived from be hydrocracked, hydrogenate and the oil of hydrofinishing, do not refine, refine and again refined oil or its mix Object.It does not refine, refine and refined oil is described in more detail in International Publication WO2008/147704, [0054]-[0056] section again Middle offer (similar disclosure provides in U.S. Patent application 2010/197536, referring to [0072]-[0073]).Naturally It is described in (similar public affairs in [0058]-[0059] section of WO2008/147704 with the more detailed description of synthetic lubricant fluid It opens content to provide in U.S. Patent application 2010/197536, referring to [0075]-[0076]).Synthetic oil also can be anti-by Fischer-Tropsch It should prepare, and the Fischer-Tropsch hydrocarbon or wax of typically hydroisomerization.In one embodiment, oil can be by Fischer-Tropsch gas extremely Prepared by liquid (gas to liquid) synthesis program and other gas are oily to liquid.
Oil with lubricant viscosity also can be such as " Appendix E-API Base Oil Interchangeability The versions of in September, 2011 of Guidelines for Passenger Car Motor Oils and Diesel Engine Oils " This, the 1.3rd part, subtitle 1.3 " Base Stock Categories " described definition.In one embodiment, there is profit The oil of sliding viscosity can be API II groups or III group oil.In one embodiment, the oil with lubricant viscosity can be API I group oil.
The amount of the existing oil with lubricant viscosity is usually that the compounds of this invention and other is being subtracted from 100 weight % The later surplus of the summation of the amount of performance additive.
Lubricating composition can be concentrate and/or prepare the form of lubricant completely.If (including addition described herein Agent) lubricating composition of the present invention is that (it can be combined with other oil to form final lubrication completely or partially for the form of concentrate Agent), then these additives with lubricant viscosity oil and/or and flux oil ratio include 1:99-99:1 weight meter or 80: 20-10:The range of 90 weight meters.
Other performance additive
Composition optionally includes other performance additive.Other performance additive may include following at least one：Metal subtracts Living agent, viscosity improver, detersive, friction improver, antiwear additive, corrosion inhibitor, dispersant, dispersant viscosity modifiers, Extreme pressure agent, antioxidant (be different from above-mentioned thioether-phenol), foam inhibitor, demulsifying agent, pour-point depressant, sealing sweller and Its mixture.These other performance additives can be in addition to the additive of public technology.For example, additive can be except public affairs It opens the corrosion inhibitor outside those, being present in described in other embodiments of technology in lubricating composition, antiwear additive and/or resists Oxidant.
Therefore, in one embodiment, public technology offer further includes following at least one lubricating composition： Dispersant, antiwear additive, dispersant viscosity modifiers, friction improver, viscosity improver (usual olefin copolymer, such as ethylene- Propylene copolymer), antioxidant (including phenol and amine antioxidants), overbased detergent (including overbased sulfonates and Phenates), extreme pressure agent, foam inhibitor, demulsifying agent, pour-point depressant, sealing sweller, or mixtures thereof.
Or mixtures thereof dispersant can be succinimide dispersants,.In one embodiment, dispersant can be used as Single dispersant exists.In one embodiment, the mixture that dispersant can be used as two or three of different dispersant exists, Wherein at least one can be succinimide dispersants.
Succinimide dispersants can be derived from least one aliphatic polyamines.Aliphatic polyamines can be ethylene, Asia Or mixtures thereof polyethylene, butylidene polyamines.In one embodiment, aliphatic polyamines can be ethylene.One In a embodiment, aliphatic polyamines can be selected from ethylenediamine, diethylenetriamines, trien, tetren, five Asias Hexamine, polyamines kettle be residual and its mixture.
Dispersant can also be derived from the material with aromatic amine.Can be that useful aromatic amine is disclosed in International Publication WO2010/062842 and (similar disclosure is provided in US2010/298185) in WO2009/064685.WO2009/ 064685 aromatic amine is usually reacted with isatoic anhydride.
Aromatic amine generally can not be heterocycle.Aromatic amine may include aniline, nitroaniline, aminocarbazole, 4-ADPA (ADPA) and the coupled product of ADPA.In one embodiment, amine can be the idol of 4-ADPA (ADPA) and ADPA Co-product.Aromatic amine may include bis- [p- (p- aminobenzene amido) phenyl]-methane, 2- (7- Amino-acridina -2- ylmethyls) - N-4- { 4- [4- (4- Amino-phenylaminos)-benzyl]-phenyl }-benzene -1,4- diamines, N- { 4- [4- (4- amino-phenyl ammonia Base)-benzyl]-phenyl -2- [4- (4- Amino-phenylaminos)-hexamethylene -1,5- diene ylmethyl]-benzene -1,4- diamines, N- [4- Or mixtures thereof (7- Amino-acridina -2- ylmethyls)-phenyl]-benzene -1,4- diamines.
Dispersant can be that N- replaces long chain alkenyl succinimides.N- replaces the example packet of long chain alkenyl succinimides Include polyisobutenyl succinimide.In general, the polyisobutene for deriving polyisobutylene succinic anhydride has 350-5000, or The number-average molecular weight of 550-3000 or 750-2500.Succinimide dispersants and its preparation are disclosed in such as United States Patent (USP) 3, 172,892、3,219,666、3,316,177、3,340,281、3,351,552、3,381,022、3,433,744、3,444, 170,3,467,668,3,501,405,3,542,680,3,576,743,3,632,511,4,234,435, Re 26,433 and 6, 165,235, in 7,238,650 and EP patent applications, 0 355 895A.
Also dispersant can be post-processed by being reacted with any one of plurality of reagents by conventional method.Wherein, this It is a bit boron compound (such as boric acid and borate), urea, thiocarbamide, dimercaptothiodiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon take Succinic anhydride, maleic anhydride, nitrile, epoxides and the phosphorus compound in generation.
Dispersant can with the 0.1 weight % to 10 weight % of lubricating composition or 2.5 weight % to 6 weight %, or 3 weight % of person to 5 weight % exists.
In one embodiment, the lubricating composition of public technology further includes dispersant viscosity modifiers.Dispersion Agent viscosity improver can be with the 0 weight % to 5 weight % of lubricating composition either 0 weight % to 4 weight % or 0.05 Weight % to 2 weight %.
Dispersant viscosity modifiers may include functionalised polyolefin, such as with acylating agent such as maleic anhydride and amine-functionalized Ethylene-propylene copolymer；With amine-functionalized polymethacrylates, or the styrene-maleic anhydride copolymer that is reacted with amine Object.The more detailed description of dispersant viscosity modifiers is disclosed in International Publication WO2006/015130 or United States Patent (USP) 4,863, 623；6,107,257；6,107,258；In 6,117,825.In one embodiment, dispersant viscosity modifiers may include United States Patent (USP) 4,863,623 (referring to the 15th row of the 2nd column to the 52nd row of the 3rd column) or International Publication WO2006/015130 (referring to [0008] section of page 2 and [0065]-[0073] section preparation embodiment) it is described those.
In one embodiment, dispersant viscosity modifiers may include United States Patent (USP) 7,790,661, the 48th row of the 2nd column To described in the 38th row of the 10th column those.7,790,661 dispersant viscosity modifiers are included (a) comprising carboxylic-acid functional or its reaction Property equivalent polymer, the polymer have more than 5,000 number-average molecular weight；(b) include at least one aromatic amine Amine component, the aromatic amine can be condensed with the carboxylic-acid functional to provide the amino and at least one of side group comprising at least one A other groups comprising at least one nitrogen, oxygen or sulphur atom, wherein aromatic amine are selected from (i) nitro substituted aniline, and (ii) includes Pass through-C (O) NR11Group ,-C (O) O- groups ,-O- groups ,-N-N- groups or-SO22 aromatic structure portions of group connection The amine divided, wherein R11For hydrogen or alkyl, an Aromatic moieties, which carry, can be condensed amino, (iii) aminoquinoline, (iv) amino Benzimidazole, (v) N, N- dialkyl phenylene diamines, and (vi) ring alpha substituted benzylamine.
In one embodiment, public technology can be the lubricating composition for further including molybdenum compound.Molybdenum chemical combination Object can be selected from the amine salt and its mixture of molybdenum dialkyl-dithiophosphate, molybdenum dithiocarbamate, molybdenum compound.Molybdenum compound Be provided to lubricating composition 0-1000ppm either 5-1000ppm either 10-750ppm either 5ppm to 300ppm or The molybdenum of 20ppm to 250ppm.
In one embodiment, public technology can be the lubricating composition for further including overbased detergent.It crosses Alkaline detersive is as known in the art.Overbased detergent can be selected from without thiophenol salt, sulfur-bearing phenates, sulfonate, Salixarate, salicylate and its mixture.
Overbased detergent may also include to be formed with mixed surfactant system, including phenates and/or sulfonate component " mixing " detersive, such as phenates/salicylate, sulfonate/phenates, sulfonate/salicylate, sulfonate/phenates/bigcatkin willow Hydrochlorate；Such as such as United States Patent (USP) 6,429,178；6,429,179；6,153,565；Described in 6,281,179.If such as using Mix sulfonate/phenate detergents, then mixing detersive is considered being equal to the phenates and sulfonate soap for introducing similar quantity respectively The amount of independent phenates and sulfonate detergent.
In general, overbased detergent can be phenates, sulfur-bearing phenates, sulfonate, salixarate and salicylate sodium, Calcium or magnesium salts.Parlkaline phenates and salicylate usually have the total base number that 180-450TBN is measured as using ASTM D2896. The overbased sulfonates usually total base number with 250-600 or 300-500.In one embodiment, sulfonate detergent Can be at least 8 metal than dominant linear alkylbenzene sulfonate detersive, such as U.S. Patent application 2005065045 Described in [0026]-[0037] section of (and authorizing US 7,407,919).Linear alkyl benzene, which can have, to be connected on linear chain Any position, the phenyl ring on usual 2,3 or 4 or its mixture.Dominant linear alkylbenzene sulfonate detersive can be used especially Fuel economy is improved in help.In one embodiment, sulfonate detergent can be one or more oil-soluble alkyl The metal salt of toluenesulfonic acid salt compound, as U.S. Patent application 2008/0119378 [0046]-[0053] section in disclose 's.Overbased detergent can be with 0 weight % to 15 weight % either 1 weight % to 10 weight % or 3 weight % to 8 weights % is measured to exist.For example, in large diesel engine, detersive can exist with the weight of 3 weight % to 5 % of lubricating composition.It is right In bus engine, detersive can exist with the weight of 0.2 weight % to 1 % of lubricating composition.
In one embodiment, lubricating composition includes at least one antioxidant.Antioxidant can be with lubrication group Either 0.1 weight % to 10 weight % or 0.5 weight % to 5 weight % exists the 0 weight % to 15 weight % of conjunction object.
Antioxidant includes olefine sulfide, alkylated diphenylamine (usual dinonyldiphenylamine, octyl diphenylamine, dioctyl Diphenylamines), phenyl-α-naphthylamine (PANA), hindered phenol, or mixtures thereof molybdenum compound (such as molybdenum dithiocarbamate).
Hindered phenol antioxidant usually contains sec-butyl and/or tertiary butyl as steric group.Phenolic groups can be further Replaced by alkyl (usually linear or branched-alkyl) and/or the bridge linkage group being connected on the second aromatic group.Suitable hindered phenol The example of antioxidant includes 2,6 di t butyl phenol, 4- methyl -2,6 di t butyl phenol, two tertiary fourths of 4- ethyls -2,6- Base phenol, 4- propyl -2,6 di t butyl phenol or 4- butyl -2,6 di t butyl phenol or 4- dodecyls -2,6- two Tert-butyl phenol.In one embodiment, hindered phenol antioxidant can be ester, and may include for example from Ciba's IrganoxTML-135.Suitable ester-containing hindered phenol antioxidant chemistry is described in more detail in United States Patent (USP) 6,559,105 It finds.
The example of suitable frictional modifier includes the long-chain fatty acid derivative, fatty ester or fat epoxide of amine；Fat The condensation product of fat imidazoline such as carboxylic acid and polyalkylene polyamine；The amine salt of alkyl phosphoric acid；Fatty alkyl tartrate；Fatty alkane Base tartrimide or fatty alkyl tartramide.
Friction improver may also include material, such as sulfurized fatty compound and alkene, molybdenum dialkyl-dithiophosphate, two The monoesters of thiocarbamic acid molybdenum, sunflower oil or polyalcohol and aliphatic carboxylic acid.
In one embodiment, friction improver may include following at least one：The long-chain fatty acid derivative of amine, length Chain fatty ester or long chain fatty epoxide；Fatty imidazolines；The amine salt of alkyl phosphoric acid；Fatty alkyl tartrate；Fatty alkane Base tartrimide；With fatty alkyl tartramide.Friction improver can with the 0 weight % to 6 weight % of lubricating composition, Either 0.05 weight % to 4 weight % or 0.1 weight % to 2 weight % exists.In one embodiment, lubricating combination Object can be free of long fatty ester (usual glyceryl monooleate).
As used herein, term " fatty alkyl " related with friction improver or " fat " mean with 10-22 carbon The carbochain of atom, usual normal carbon chain.Alternatively, fatty alkyl can be mono-branched alkyl, branched usually on β-position.Single branch The example for changing alkyl includes 2- ethylhexyls, 2- propylheptyls or 2- octyldodecyls.
In one embodiment, friction improver may include following at least one：Long-chain fatty acid derivative, the fat of amine Fat ester or fat epoxide；Fatty alkyl citrate；Fatty alkyl tartrate；Fatty alkyl tartrimide；And fat Fat alkyl tartrate amide.
In one embodiment, friction improver can be long-chain fatty acid ester.In another embodiment, long-chain fat Fat acid esters can be monoesters, and in another embodiment, long-chain fatty acid ester can be triglycerides.
Other performance additive such as corrosion inhibitor includes those described in 5-8 sections of WO2006/047486, octyl decoyl The condensation product of amine, dodecenyl succinic acid or acid anhydride and aliphatic acid such as oleic acid and polyamines.In one embodiment, corrosion suppression Preparation includes(registered trademark of The Dow Chemical Company) corrosion inhibitor.It is rotten Corrosion inhibitor can be the homopolymer or copolymer of propylene oxide.Corrosion inhibitor is described in greater detail in The In the product pamphlet of Form No.118-01453-0702AMS published by Dow Chemical Company.Product pamphlet Title be " SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications”。
Metal deactivator includes the derivative (usual tolyl-triazole) of benzotriazole, dimercaptothiodiazole derivative, 1, 2,4- triazoles, two thio benzothiazole of benzimidazole, two Thiobenzimidazole of 2- alkyl or 2- alkyl.
In one embodiment, in addition to azoles-acrylic acid adduct described herein, above-mentioned corrosion inhibitor and gold can be used Belong to passivator.In yet another embodiment, above-mentioned corrosion inhibitor and metal deactivator can use azoles described herein-acrylic acid adduction Object replaces.
Foam inhibitor includes polysiloxanes or ethyl acrylate and 2-EHA and optional vinyl acetate Copolymer.Demulsifying agent includes trialkylphosphate, polyethylene glycol, polyethylene glycol oxide, polypropylene oxide and (ethylene oxide-oxygen Change propylene) polymer.Pour-point depressant includes the ester, polymethacrylates, polyacrylate or poly- of maleic anhydride-styrene Acrylamide.
In different implementation scenarios, lubricating composition can have composition as described in the following table 1.Weight percent (weight Measure %) it is based on active material.
Table 1
Commercial Application
Lubricating composition can be used in internal combustion engine.Engine or engine pack can be made of the alloy comprising lead or copper. Engine pack can have steel or aluminium surface (usual steel surface).
Aluminium surface can be derived from aluminium alloy, can be eutectic or hypereutectic aluminium alloy (such as derived from alumina silicate, alumina Those of compound or other ceramic materials).Aluminium surface may be present in cylinder barrel with aluminium alloy or aluminium compound, cylinder block or On piston ring.
Internal combustion engine can be with or without scheme for exhaust gas circulation system.Internal combustion engine can be equipped with emission control systems or turbocharging Device.The example of emission control systems includes diesel particulate filter (DPF), or uses the system of selective catalytic reduction (SCR).
In one embodiment, internal combustion engine can be diesel-fueled engine (usual large diesel engine), Fuel Petroleum Engine, natural gas fueled engines or blend gasoline/alcohol engine.In one embodiment, internal combustion engine can be Diesel-fueled engine is in another embodiment gasoline engines.In one embodiment, internal combustion engine can be Large diesel engine.
Internal combustion engine can be 2 strokes or 4 Stroke Engines.Suitable internal combustion engine includes marine diesel, aviation piston Formula engine, low load diesel engine and automobile and motortruck engine.
Lubricant compositions for internal combustion engine may be adapted to any engine lubricant but regardless of sulphur, phosphorus or sulfate ash (ASTM D-874) content.The feature of lubricating composition can be at least one of following：(i) 0.2 weight % to 0.4 weight % or less sulfur contents, the phosphorus content of (ii) 0.08 weight % to 0.15 weight %, and (iii) 0.5 weight % are measured to 1.5 weights Measure % or less sulfate ash contents.The feature of lubricating composition can be with：(i) 0.5 weight % or less sulphur contains Amount, (ii) 0.1 weight % or less phosphorus contents, and (iii) 0.5 weight % contain to 1.5 weight % or less sulfate ashes Amount.
In one embodiment, the feature of lubricating composition can be with 0.5 weight % to the sulfuric acid of 1.2 weight % Salt ash content.
Some known above-mentioned materials may interaction in final preparaton so that the component of final preparaton may be with Originally those of addition difference.For example, metal ion (such as detersive) it can migrate to the other acid or cloudy of other molecules Ion position.The product being consequently formed, the product formed when being included in using disclosed composition may be not easy to describe.So And all such improvement and reaction product are included within the scope of the present invention, disclosed composition includes by by above-mentioned group Divide and/or material mixes and the product of formation.
Following embodiment provides the elaboration to the present invention.These embodiments are non-exhaustive and are not intended to limit the present invention Range.
Embodiment
The preparation of thioether-phenol
Following embodiment shows the non-limiting technology for preparing thioether-phenol as described above.
Embodiment A-1
2- (dodecylthio) ethyl alcohol (453g, 1 mole), 3- (3,5- di-t-butyl -4- oxybenzenes will be packed into 2-L flasks Base) butyl propionate (627g, 1.02 moles) and butanol titanium (Ti (OBu)4) (1.6g, 0.0025 mole).As stirring will mixing Object is heated to 185 DEG C.It holds the mixture at 185 DEG C so that component reaction.Butanol is removed during reaction process.Work as collection When the butanol of theoretical amount (after about 7 hours), mixture is cooled down, and collect the product as brown liquid.
Embodiment A-2
2- (dodecylthio) butanol (1 equivalent), 3- (3,5- di-t-butyl -4- hydroxyphenyls) third will be packed into 2-L flasks Acid butyl ester (1.02 equivalent) and butanol titanium (Ti (OBu)4) (0.0025 equivalent).As stirring heats the mixture to 185 DEG C.It will Mixture is maintained at 185 DEG C so that component reaction.Butanol is removed during reaction process.When the butanol of collection theory amount (after about 7 hours), mixture are cooled down, and collect the product as brown liquid.
Lubricant embodiment EX0-EX5
It is peace and quiet using conventional additives, including polymeric viscosity modifier, ashless succinimide dispersants, parlkaline Agent, antioxidant (combination of phenol ester, diaryl amine and olefine sulfide), zinc dialkyl dithiophosphate (ZDDP) and other The conventional additives of performance additive prepare a series of 5W-30 engine lubricants with lubricant viscosity.All lubricants are all It is prepared by the general preparaton in such as the following table 2.
Table 2-lubricant oil composite basic formula agent1
Benchmark (weight %)
II group base oils 100% surplus
Overbased detergent2 0.77
Zinc dialkyl dithiophosphate 0.86
Antioxidant 1.85
Active dispersing agents3 6.23
Viscosity improver 1.12
Other additives4 0.18
% phosphorus 0.75
1. all concentration are all based on oil-free (being based on active material)
2. alkyl sulfonic acid calcium
3. 2000MnPIB succinimide dispersants
4. other additives include friction improver, foam inhibitor etc.
Then thioether-phenol of embodiment A-1 and A-2 are added with being measured shown in table 3 in reference oil.Amount is based on activity Total weight of the substance based on lubricant oil composite.
Table 3-lubricant oil composite preparaton
Embodiment A-1 (weight %) A-2 (weight %)
BL1
EX1 0.78
EX2 0.78
It is tried using pressure differential scanning calorimetry (PDSC), micro coking test (MCT) and little Song heat pipes (KHT) oxidation rack Test the lubricant oil composite in assessment table 3.
PDSC assesses the inoxidizability or stability of lubricating oil by measuring oxidation induction time (OIT).OIT is in isothermal Under the conditions of oil become exposed to oxygen and start oxidation between time.Therefore, OIT is longer, and oily inoxidizability is bigger.PDSC numbers According to using for predicting that the CEC L-85-99 test procedures of the lubricant properties in large diesel engine obtain.
When lubricant evaporation or thermal degradation, lubricant forms the tendency of deposit or residue for MCT assessments.By the small of oil Sample is placed on metallic plate.Then the difference on metallic plate is separately heated to 280 DEG C (" hot temperature ") and 230 DEG C of (" cold temperature Degree ").Then the carbon deposits of visual inspection metallic plate or residue and and Comparison of standards.Then commenting the value with 1-10 Each sample is distributed to, wherein 1 has most residues, and 10 have minimal amount of residue.Therefore, higher in MCT Scoring mean preferable sediment monitoring performance.Details about MCT can be in entitled " Microcoking Test for It is found in the standardization program of Automotive Lubricants ", GFC Lu-27-A-13Issue 2.
KHT is tested, glass tube is inserted into aluminum heater block and is heated to 280 DEG C.Then it will be tried by syringe pump Sample is with 0.31cm3The flow velocity and 10cm of/hr3The air velocity pumping of/min passes through glass tube 16 hours.In off-test, Pipe is rinsed and with the grade visual evaluation of 0-10, wherein 0 is clarinet, and 10 be clean pipe.
KHT measures the deposit formability of lubricant under the high temperature conditions.In KHT, higher scoring means preferably Sediment monitoring performance.The result obtained about each lubricant is shown in table 4.
Table 4
Embodiment KHT 280℃ L-85-99OIT min MCT
BL1 2 115 6.64
EX1 7 145 8.67
EX2 7 138 7.09
As a result lubricating composition of the display comprising disclosed thioether-phenol is provided improves compared with benchmark preparaton (BL1) Antioxygenic property, while reducing deposit and being formed.
Lubricant embodiment EX3 to EX4
Using including polymeric viscosity modifier, ashless succinimide dispersants, overbased detergent, antioxidant (combination of phenol ester, diaryl amine and olefine sulfide), dithio dialkyl phosphonic acid zinc (ZDDP) and other performance additive Conventional additives prepare the 5W-30 engine lubricants with lubricant viscosity of second series.All lubricants are all by as follows It is prepared by the general preparaton in table 5.
Table 5-lubricant oil composite basic formula agent1
Benchmark
II group base oils To 100% surplus
Overbased detergent2 0.77
Zinc dialkyl dithiophosphate 0.86
Antioxidant 0.85
Active dispersing agents3 6.23
Viscosity improver 1.12
Other additives4 0.18
% phosphorus 0.75
1. all concentration are all based on oil-free (being based on active material)
2. alkyl sulfonic acid calcium
3. 2000MnPIB succinimide dispersants
4. other additives include friction improver, foam inhibitor etc.
Then by commercially available phenolic antioxidants (Irganox L-135) and thioether-phenol of embodiment A-1 and A-2 It is added in reference oil with being measured shown in table 6.Amount is based on total weight of the active material based on lubricant oil composite.
Table 6-lubricant oil composite preparaton
Irganox L-135 A-1 A-2
Comp1 1
EX3 1
EX4 1
It is tried using pressure differential scanning calorimetry (PDSC), micro coking test (MCT) and little Song heat pipes (KHT) oxidation rack Test the lubricant oil composite in assessment table 6.The result obtained about each lubricant is shown in table 7.
Table 7
Embodiment KHT 280℃ L-85-99OIT min MCT
Comp1 2 115 6.64
EX3 7 160 8.11
EX4 5 141 7.34
As a result lubricating composition of the display comprising disclosed thioether-phenol provides and includes commercially available phenolic antioxidants The comparative example (Comp1) of Irganox L-135 compares improved antioxygenic property, while reducing deposit and being formed.
Lubricant embodiment EX5-EX6
Using including polymeric viscosity modifier, ashless succinimide dispersants, overbased detergent, antioxidant (combination of phenol ester, diaryl amine and olefine sulfide), dithio dialkyl phosphonic acid zinc (ZDDP) and other performance additive Conventional additives prepare third series the 5W-30 engine lubricants with lubricant viscosity.All lubricants are all by as follows It is prepared by the general preparaton in table 8.
Table 8-lubricant oil composite basic formula agent1
Benchmark
II group base oils To 100% surplus
Overbased detergent2 1.0
Zinc dialkyl dithiophosphate 0.86
Antioxidant 0.85
Active dispersing agents3 6.23
Viscosity improver 1.12
Other additives4 0.18
% phosphorus 0.75
1. all concentration are all based on oil-free (being based on active material)
2. the mixture of alkyl sulfonic acid calcium and alkylphenol calcium
3. 2000Mn PIB succinimide dispersants
4. other additives include friction improver, foam inhibitor etc.
Then by commercially available phenolic antioxidants (Irganox L-135) and thioether-phenol of embodiment A-1 and A-2 It is added in reference oil with being measured shown in table 9.Amount is based on total weight of the active material based on lubricant oil composite.
Table 9-lubricant oil composite preparaton
Irganox L-135 A-1 A-2
Comp2 1
EX5 1
EX6 1
It is tried using pressure differential scanning calorimetry (PDSC), micro coking test (MCT) and little Song heat pipes (KHT) oxidation rack Test the lubricant oil composite in assessment table 8.The result obtained about each lubricant is shown in table 10.
Table 10
Embodiment KHT 280℃ L-85-99OIT min MCT
Comp2 2 116 7.23
EX5 3 152 8.26
EX6 3 140 7.36
As a result lubricating composition of the display comprising disclosed thioether-phenol provides and includes commercial phenol antioxidant The control formulation (Comp2) of Irganox L-135 compares improved antioxygenic property, while reducing deposit and being formed.
Some known above-mentioned materials may interaction in final preparaton so that the component of final preparaton may be with Originally those of addition difference.For example, metal ion (such as detersive) it can migrate to the other acid or cloudy of other molecules Ion position.The product being consequently formed, the product formed when being included in its intended use using the present composition may not It is easy description.However, all such improvement and reaction product are included within the scope of the present invention；The present invention will be upper including passing through The composition stated component mixing and prepared.
Although showing certain representative embodiments and details to illustrate the present invention, skilled in the art realises that can not Deviate the scope of the present invention and makes various changes and the improvement of this paper.On this point, the scope of the present invention is only by following power Sharp claim limitation.

Claims (15)

1. a kind of lubricating composition, it includes：
A. the oil with lubricant viscosity；With
B. thioether fortified phenol (" thioether-phenol "),：
I. include the reaction product of thioether substituted alcohols or thioether substitution amine and the phenol at least one side acyl group；And
Ii. have at least 1:1 methylthio group:Phenolic groups ratio.
2. lubricating composition according to claim 1, wherein thioether-phenol have structure：
Wherein m is the integer of 0-3；N is the integer of 1-2；P is the integer of 1-20；Each R1It independently is hydrogen or C1-C20Alkyl, or Person when m be more than 1 when, two alkyl together when can form saturation or unsaturation ring containing 5-6 carbon atom；R2For C1-C6Hydrocarbon Base；R3For C1-C20Alkyl；R4For C1-C32Alkyl；X is O or NR5；And R5For hydrogen or C1-C24Alkyl, condition are when X is NR5When, Then p is 1.
3. lubricating composition according to claim 2, wherein at least one R1For C1-C4Alkyl；R3For C1-C20Alkyl；X is O；And P is the integer of 1-12.
4. according to the lubricating composition of claim 1-3, wherein thioether-phenol has structure：
Wherein R3For C1-C20Alkyl；R4For C1-C32Alkyl；R6For hydrogen or C1-C12Alkyl；And R7And R8It independently is hydrogen or C1-C20 Alkyl or when together, R7And R8Saturation or unsaturation ring containing 5-6 carbon atom can be formed.
5. lubricating composition according to claim 4, wherein R6And R7At least one of be tertiary butyl.
6. lubricating composition according to claim 4, wherein R6And R7All it is tertiary butyl.
7. according to the lubricating composition of claim 2-6, wherein R4For C1-C18Alkyl.
8. according to the lubricating composition of claim 2-7, wherein R3For C2-C4Alkyl.
9. lubricating composition according to claim 1 the, wherein thioether-phenol includes following at least one：3- (bis- uncles of 3,5- Butyl -4- hydroxyphenyls) propionic acid 2- (butylthio) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (butylthio) propyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (butylthio) butyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (own sulfenyl) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (own sulfenyl) propyl ester, 3- (3,5- di-t-butyl -4- hydroxyls Phenyl) propionic acid 2- (own sulfenyl) butyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (pungent sulfenyl) ethyl ester, 3- (3,5- bis- Tertiary butyl -4- hydroxyphenyls) propionic acid 2- (pungent sulfenyl) propyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (pungent sulfenyl) fourth Ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (last of the ten Heavenly stems sulfenyl) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (last of the ten Heavenly stems sulfenyl) propyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (last of the ten Heavenly stems sulfenyl) butyl ester, 3- (3,5- di-t-butyls -4- Hydroxyphenyl) propionic acid 2- (dodecylthio) ethyl ester, 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (dodecylthio) third Or mixtures thereof ester or 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid 2- (dodecylthio) butyl ester,.
10. according to the lubricating composition of any one of the preceding claims, at least one nitrogenous dispersant is further included.
11. according to the lubricating composition of any one of the preceding claims, at least one overbased detergent is further included.
12. according to the lubricating composition of any one of the preceding claims, it includes the total weights based on the lubricating composition Thioether-phenol described in 0.01 weight % to 5 weight %.
13. a kind of method of lubricating internal combustion engines comprising make internal combustion engine and the lubrication group according to any one of the preceding claims Close object contact.
14. thioether-phenol reduces oxidation in the lubricating composition according to any one of claim 1-12, reduces deposit shape At and/or assist in keeping the lubricating composition total base number (TBN) purposes.
15. a kind of deposit reduced in internal combustion engine is formed and/or corrosion (keeps TBN that can reduce corrosion, correctly) method, It includes that internal combustion engine is made to be contacted with according to the lubricating composition of any one of claim 1-12.
CN201680072001.4A 2015-11-11 2016-11-08 The lubricating composition of Sulfide-containing Hindered 5-substituted phenol compounds Pending CN108473899A (en)

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